WO2019079457A2 - Exfoliation en phase liquide anhydre de nanofeuilles ges électrochimiquement actives de pristine - Google Patents

Exfoliation en phase liquide anhydre de nanofeuilles ges électrochimiquement actives de pristine Download PDF

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WO2019079457A2
WO2019079457A2 PCT/US2018/056296 US2018056296W WO2019079457A2 WO 2019079457 A2 WO2019079457 A2 WO 2019079457A2 US 2018056296 W US2018056296 W US 2018056296W WO 2019079457 A2 WO2019079457 A2 WO 2019079457A2
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ges
few
fluid medium
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WO2019079457A3 (fr
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Mark C. Hersam
David Lam
Kan-Sheng Chen
Joohoon Kang
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Northwestern University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G17/00—Compounds of germanium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • germanium sulfide As a layered IV- VI semiconducting compound that is isostructural to BP, germanium sulfide (GeS) has been studied in its bulk layered form, but is a recent addition to the family of 2D materials. In addition, germanium -based materials such as GeS are ideal for lithium-ion (Li-ion) batteries due to germanium's high theoretical capacity of 1620 mAhg "1 .
  • M0S2 exhibits capacities of over 800 mAhg "1 for both bulk and exfoliated anodes, but after 50 cycles, the capacity of bulk M0S2 decreases to 226 mAhg "1 while exfoliated M0S2 retains high capacities over 750 mAhg "1 .
  • GeS is a promising material for photovoltaics and photodetectors due to a semiconducting band gap of -1.6 eV and high photoresponsivity of -200 AW "1 . Thin layers of GeS would further optoelectronic applications by opening up opportunities for gate-tunability.
  • micromechanical exfoliation are hindered by exceptionally low yields and throughput.
  • the present invention can provide a method of preparing or using an anhydrous fluid medium to prepare few-layer germanium sulfide.
  • a method can comprise providing a composition comprising bulk germanium sulfide and an anhydrous fluid medium; and sonicating such a composition to provide a medium comprising at least partially exfoliated nanomaterials comprising few-layer germanium sulfide as discussed elsewhere herein, having a thickness dimension selected from up to about 5 nm, about 5 - about 10 nm and up to or greater than about 15 nm and combinations of such thickness dimensions.
  • such a fluid medium can comprise a solvent chosen to avoid, inhibit, reduce and/or otherwise modulate germanium sulfide degradation, having a surface
  • such a fluid medium can comprise N-methyl-2-pyrrolidone, dimethylformamide, dimethyl sulfoxide or other high- boiling solvents.
  • the present invention can also provide a method of preparing few- layer germanium sulfide.
  • a method can comprise providing a composition comprising bulk crystalline germanium sulfide and a medium comprising anhydrous N-methyl-2-pyrrolidone; sonicating such a composition to provide such a medium comprising at least partially exfoliated germanium sulfide nanomaterials; and, optionally, centrifuging and/or density gradient centrifuging such a medium to provide a supernatant component comprising few-layer germanium sulfide, as discussed above.
  • the resulting germanium sulfide nanosheets can be incorporated into thin-film devices, such as but not limited to alkali metal ion anodes, cells and batteries.
  • the present invention can also provide a composition comprising a few-layer germanium sulfide nanomaterial comprising at least one of mono-, bi-, tri- and n-layer few-layer germanium sulfide, where n can be 4 - about 10 and such layer(s) can be in
  • anhydrous medium comprising N-methyl-2-pyrrolidone.
  • the present invention can also be directed to an electronic device comprising a substrate and coupled thereto a component comprising a few-layer germanium sulfide nanomatenal of this invention.
  • a substrate can be a current collector, and such a component can independently comprise such a germanium sulfide nanomaterial and carbon black.
  • a device can be a lithium ion battery comprising a cell comprising a germanium sulfide anode of the sort described herein, a metallic lithium cathode and a lithium ion electrolyte therebetween.
  • FIG. 1A-F Schematic diagram of the sealed-tip ultrasonication apparatus. Teflon tape is wrapped around the lip of the centrifuge tube and Parafilm is wrapped around the cap and tip to minimize exposure to ambient conditions during ultrasonication.
  • C Bright- field TEM micrograph of a GeS nanosheet.
  • D Concentration of exfoliated powder GeS as a function of solvent surface tension after centrifugation at 1,000 rpm for 10 minutes. The concentration of NMP-exfoliated crystal GeS is plotted as a reference.
  • E UV-Vis spectra of GeS exfoliated in solvents of different surface tensions and centrifuged at 1,000 rpm for 10 minutes.
  • FIG. 2A-F Figures 2A-F.
  • A AFM micrograph of nanosheets drop-cast onto a 300 nm SiC /Si substrate.
  • B Low magnification TEM image of nanosheets.
  • C Thickness
  • Figures 3A-B XPS of LPE-processed GeS nanosheets for the core levels of (A) Ge 3d and (B) S 2p.
  • the as-exfoliated material shows a small oxide peak, which does not increase substantially following centrifugation.
  • Figures 4A-C (A) URTEM micrograph, (B) atomic structure, and
  • FIG. 5A-D (A) Voltage profile of the LPE-processed GeS anode at 0.2 C. (B) Specific capacity as a function of cycle index. The capacity stabilizes within 10 cycles. (C) Specific capacity as a function of cycle rate after stabilization. The electrode maintains a high specific capacity (231 mAh g "1 ) at 10 C, showing excellent rate capability. (D) Literature comparison with other LPE or chemically exfoliated 2D materials serving as the active material in Li-ion battery anodes.
  • Li-ion battery anodes based on LPE-processed GeS show exceptional rate performance with high capacity retention.
  • literature references [24] J. Xiao, D. Choi, L. Cosimbescu, P. Koech, J. Liu, J. P. Lemmon, Chem. Mater. 2010, 22, 4522; [43] R. Bhandavat, L. David, G. Singh, J. Phys. Chem. Lett. 2012, 3, 1523;
  • Figures 6A-B XPS of the bulk GeS crystal for the core levels of (A) Ge 3d and (B) S 2p.
  • the GeS peaks at 29.7 eV and 30.2 eV in the Ge 3d spectrum match those found in the LPE-processed GeS nanosheet sample.
  • the GeS peaks found in the S 2p spectrum at 161.2 eV and 162.4 eV correspond to the peaks observed in the LPE-processed GeS nanosheet sample.
  • the oxide peak found in the Ge 3d spectrum has a peak position at 32.5 eV, which matches the position of Ge0 2 .
  • the present invention provides an efficient LPE approach to 2D GeS nanosheets based on ultrasonication in an anhydrous medium such as N-methyl-2-pyrrolidone using a customized sealed-tip sonication system.
  • the resulting GeS nanosheets possess high structural and chemical integrity with superlative electrochemical properties, particularly enabling exceptional capacity retention and high-rate performance in Li-ion battery anodes.
  • a sealed ultrasonication apparatus is employed to limit ambient exposure, as shown in Figure 1 A. (See, Example 1 below.) Ultrasonication shears the GeS crystal along the b-plane ( Figure IB), resulting in thin nanosheets.
  • GeS powder is exfoliated in solvents of different surface tensions (Ethanol: 22.1 mN/m, Acetone: 25.2, Isopropanol (IP A): 23, Hexane: 18.43, Chloroform: 27.5, Dimethyl formamide (DMF): 37.1, anhydrous N-Methyl-2-pyrrolidone ( MP): 40.79).
  • 7.5 mg of GeS powder and 15 mL of solvent of are placed in the apparatus and sonicated in an ice bath at -50 W for 1 hr and are subsequently centrifuged at 500 or 1,000 rpm for 10 minutes.
  • ICP-MS inductively coupled plasma mass spectrometry
  • NMP is a usefjul solvent to exfoliate GeS
  • 7.5 mg of GeS crystal and 15 mL of anhydrous NMP are placed in the apparatus and sonicated in an ice bath at -50 W for 1 hour. Under these conditions, the GeS crystal is sheared along the b-plane, resulting in thin nanosheets, as confirmed by atomic force microscopy (AFM) and transmission electron microscopy (TEM) ( Figure C).
  • AFM atomic force microscopy
  • TEM transmission electron microscopy
  • Raman spectroscopy on the GeS nanosheets shows peaks that correspond to the A 3 g (112 cm -1 ), B 3 g (213 cm -1 ), A l g (240 cm -1 ), and A 2 g (270 cm -1 ) modes of the parent GeS crystal, which suggests that the exfoliation process does not introduce significant structural or chemical degradation (Figure F).
  • the B 3g mode corresponds to the in- plane shear vibration of parallel layers in the zigzag direction (the c-axis in Figure IB), while the A g modes correspond to shear vibration of parallel layers in the armchair direction (a-axis).
  • the positions of the Raman peaks in the exfoliated GeS agree well with those of the parent crystal with similar peak widths, which suggests that exfoliation does not introduce significant structural degradation.
  • the resulting dispersion is characterized via AFM and TEM for thickness and lateral length histograms, respectively.
  • AFM samples are prepared by drop-casting the resulting solution on a SiC /Si substrate ( Figure 2A) while TEM samples are prepared by depositing a drop on a copper grid with a Formvar/carbon film
  • ICP-MS Inductively coupled plasma mass spectrometry
  • X-ray photoelectron spectroscopy was conducted on both the as- sonicated and centrifuged dispersions.
  • Figure 3 A shows the Ge 3d XPS spectra, with a doublet assigned to binding energies of 29.7 eV and 30.3 eV for the 3d 5/2 and 3d 3/2 GeS peak, respectively, and a singlet assigned to 31.2 eV for the GeO peak.
  • the GeS doublet indicates that the solution-processed GeS is of high chemical quality (see Figure 6 for comparison XPS on the bulk crystal), with the smaller GeO peak attributed to surface oxide.
  • the S 2p peaks confirm the presence of GeS, with a GeS doublet assigned to 161.2 eV and 162.4 eV for the 2p 3/2 and 2p 1/2 peaks, respectively, and an oxide-containing doublet assigned to 161.8 eV and 162.9 eV. Centrifugation does not noticeably alter the shape of the XPS spectra, indicating that the refined dispersion remains primarily pristine GeS, as verified by XPS quantitative analysis (available, but not shown).
  • TEM further confirms the crystalline structure of LPE-processed GeS.
  • Figures 4A-B shows a high-resolution TEM (HRTEM) micrograph of a GeS nanosheet and the corresponding GeS crystal lattice viewed along the out-of-plane direction.
  • HRTEM high-resolution TEM
  • SAED selected-area electron diffraction
  • the first discharge and charge capacities are 2,295 mAhg “1 and 1, 166 mAhg “1 respectively, corresponding to an initial Coulombic efficiency of 51% from the irreversible conversion of GeS into Ge and Li 2 S. After 10 cycles, the charge retention stabilizes with discharge and charge capacities of
  • Figure 5B shows the long-term cycling stability where the charge capacity of the GeS/PVDF/CB anode is allowed to stabilize at 0.5 C, after which it is run at 1 C and finally at 1.5 C.
  • the specific capacity at 1.5 C does not decrease with increasing cycle number and stabilizes at a value of 769 mAhg "1 at 1,000 cycles.
  • Figure 5C further shows the specific capacity as a function of cycling rate.
  • the GeS anode maintains a high specific capacity of 231 mAhg "1 , illustrating the viability of GeS nanosheet anodes for high current density operation.
  • This superlative performance may be due to lower energy barriers to diffusion as well as the shorter lateral distances needed for lithium ions to diffuse into GeS nanosheets.
  • the battery recovers to its stabilized value at 0.2 C.
  • these metrics compare favorably with other LPE or chemically exfoliated 2D materials in Li-ion battery anodes (with more in-depth information in Example 6 at Table 1, below), particularly showing much higher rate performance.
  • the excellent charge retention and cycling stability of the LPE-processed GeS nanosheets Li-ion battery anodes are believed to stem from the nanostructured and electrochemically pristine nature of the material.
  • lower-dimensional materials such as GeS nanosheets are believed to demonstrate better performance than their bulk counterparts—due, at least in part, to larger surface-volume ratios and short Li + diffusion lengths.
  • ultrasonication apparatus was prepared by puncturing the plastic lid of a 50 mL conical centrifuge tube and inserting a 0.125-inch sonicator tip in the puncture. The tip and lid were sealed by wrapping Parafilm around the puncture. Teflon tape was wrapped around the threading of the centrifuge tube to further minimize ambient exposure.
  • 7.5 mg of GeS powder and 15 mL of the studied solvent were added to the tube in ambient.
  • 7.5 mg of higher-quality GeS crystal and 15 mL of anhydrous N-methyl-2-pyrrolidone ( MP) (Sigma-Aldrich) were added to the vial in the N 2 glovebox.
  • the sealed vial was then connected to the sonicator (Fisher Scientific Model 500 Sonic Dismembrator) in ambient conditions, and the GeS crystal was exfoliated via ultrasonication for 1 hour at -50 W.
  • the supernatant of the resulting dispersion was collected for use in subsequent experiments, either as-exfoliated or centrifuged with a tabletop centrifuge (Eppendorf Mircocentrifuge 5424) at 500 rpm for 10 minutes.
  • ICP-MS samples were prepared by digesting 30 ⁇ . of GeS in NMP in 450 ⁇ . of 70% HN0 3 overnight in a 65 °C silicon oil bath. After digestion, the solution was diluted with 14.52 mL of DI H 2 0 for a total dilution factor of 500. Concentrations were measured using a Thermo iCAP Q Inductively Coupled Plasma Mass Spectrometry and are the average of three measurements.
  • the concentrations for GeS exfoliated in other solvents are then calculated using the absorbance at 600 nm and the estimated value of %oo nm.
  • Raman Spectroscopy Samples for Raman spectroscopy were prepared by vacuum filtration of 1 mL of the GeS nanosheet dispersion through an anodized alumina membrane (Whatman Anodisc, 25 mm diameter, 0.02 ⁇ pore size). Raman spectra on both the bulk crystal and the exfoliated sample were collected using a Horiba LabRAM HR Evolution with an excitation wavelength of 473 nm at 0.1 mW for 60 seconds with a 2400 g/mm grating.
  • AFM samples were prepared in ambient conditions by drop-casting the GeS nanosheet dispersion onto a 300 nm SiC /Si substrate and annealing on a hotplate at 250° C until the solvent dried off.
  • AFM height and amplitude measurements were performed in tapping mode using an Asylum Cypher S AFM with Si cantilevers at -300 kHz resonant frequency. Images were taken with a scan rate of ⁇ 1 Hz and 512 pixels per line. For the as-prepared thickness and lateral length histograms, 628 flakes were considered, while for the 500 rpm histograms, 471 flakes were considered.
  • X-Ray Photoelectron Spectroscopy X-Ray Photoelectron Spectroscopy. XPS samples were prepared using the same procedure as for Raman spectroscopy. XPS measurements were performed using a high vacuum Thermo Scientific ESCALAB 250 Xi + XPS system at a base pressure of -lxlO "8 Torr using an Al Ka X-ray source (-1486.6 eV) with a 900 ⁇ spot size and a 0.1 eV binding energy resolution. All presented core-level spectra are the average of five scans taken with a dwell time of 100 ms and a pass energy of 15 eV.
  • Samples were charge compensated using a flood gun, and all core-level spectra were charge corrected to adventitious carbon at -284.8 eV. All subpeaks were fit using the software suite Avantage (Thermo Scientific). The peak assigned to GeS in the Ge 3d core-level spectra was fit with doublets, while the peaks assigned to oxides of germanium were fit with single peaks. All peaks in the S 2p core-level spectra were fit with doublets.
  • the electrolyte was 1M LiFP 6 dissolved in an organic solvent consisting of dimethyl carbonate and ethylene carbonate in a 1 : 1 volume ratio.
  • Metallic lithium was used as the counter electrode.
  • Galvanostatic charge/discharge measurements were carried out with a voltage range from 0.01 V to 2.5 V vs. Li/Li+, using an Arbin battery test station (Model BT-2143).
  • MoS 2 -Graphene 50 cycles, 225 mAhg "1 MoS 2 -rGO: 50 cycles, 750 mAhg "1 (100 mAg "1 )
  • the present invention demonstrates an effective method for LPE of pristine GeS nanosheets.
  • exfoliation of GeS is achieved, for instance, in anhydrous NMP with minimal exposure to ambient atmosphere, thus preventing chemical or structural degradation.
  • the chemical and structural integrity of the resulting nanosheets is confirmed by AFM, Raman, XPS, and TEM, revealing sub-10 nm thick GeS nanosheets with excellent crystallinity.
  • Superlative electrochemical performance is verified by incorporating the GeS nanosheets into Li-ion battery anodes, resulting in high cycling stability up to 1,000 cycles and excellent rate capability up to 10 C.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
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  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'exfoliation en phase liquide anhydre de sulfure de germanium pour obtenir du sulfure de germanium à peu de couches, peut être incorporée dans des dispositifs électroniques tels que, sans s'y limiter, des batteries et des éléments comprenant de tels matériaux.
PCT/US2018/056296 2017-10-20 2018-10-17 Exfoliation en phase liquide anhydre de nanofeuilles ges électrochimiquement actives de pristine WO2019079457A2 (fr)

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CN113753870A (zh) * 2021-09-30 2021-12-07 海南大学 一种锂离子电池用GeP纳米片负极及其超声波辅助快速剥离制备方法

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WO2011020035A2 (fr) 2009-08-14 2011-02-17 Northwestern University Tri de nanomatériaux bidimensionnels selon leur épaisseur
US9221064B2 (en) 2009-08-14 2015-12-29 Northwestern University Sorting two-dimensional nanomaterials by thickness
ES2955519T3 (es) * 2011-06-23 2023-12-04 Molecular Rebar Design Llc Baterías de iones de litio que usan nanotubos de carbono discretos, métodos para su producción y productos obtenidos a partir de ellas
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WO2014015335A1 (fr) * 2012-07-20 2014-01-23 Board Of Regents, The University Of Texas System Matériaux d'anode pour batteries li-ion
KR101400524B1 (ko) * 2012-12-26 2014-05-30 고려대학교 산학협력단 리튬이차전지의 성능 향상을 위한 황화저마늄 나노입자의 제조방법
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CN113753870A (zh) * 2021-09-30 2021-12-07 海南大学 一种锂离子电池用GeP纳米片负极及其超声波辅助快速剥离制备方法
CN113753870B (zh) * 2021-09-30 2023-05-26 海南大学 一种锂离子电池用GeP纳米片负极及其超声波辅助快速剥离制备方法

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